Designation: E291 − 09

Standard Test Methods for

Chemical Analysis of Caustic Soda and Caustic Potash
(Sodium Hydroxide and Potassium Hydroxide)1
This standard is issued under the fixed designation E291; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope* bility of regulatory limitations prior to use. Specific hazard

1.1 These test methods cover only the analyses usually statements are given in Section 6.
required on the following commercial products: 2. Referenced Documents
1.1.1 Caustic soda (sodium hydroxide), 50 and 73 % li-
quors; anhydrous (solid, flake, ground, or powdered), and 2.1 ASTM Standards:2
1.1.2 Caustic potash (potassium hydroxide), 45 % liquor; D1193 Specification for Reagent Water
anhydrous (solid, flake, ground, or powdered). E60 Practice for Analysis of Metals, Ores, and Related
Materials by Spectrophotometry
1.2 The analytical procedures appear in the following order: E180 Practice for Determining the Precision of ASTM
Alkalinity (Total), Titrimetric (for 50 to 100 % 8 to 14 Methods for Analysis and Testing of Industrial and Spe-
NaOH and 45 to 100 % KOH)
cialty Chemicals (Withdrawn 2009)3
Carbonate, Gas-Volumetric (0.001 g CO2, min) 15 to 24
Carbonate, Gravimetric (0.001 g CO2, min) 25 to 33 E200 Practice for Preparation, Standardization, and Storage
Chloride, Titrimetric, (0.001 g Cl−, min) 34 to 40 of Standard and Reagent Solutions for Chemical Analysis
Chloride, Potentiometric Titration (0.3 to 1.2 %) 41 to 47
Chloride, Ion Selective Electrode (0.6 to 120 µg/g) 48 to 55 3. Significance and Use
Iron, Photometric (0.005 mg Fe, min) 56 to 64
Sulfate, Gravimetric, (0.002 g SO3, min) 65 to 71 3.1 Caustic soda and caustic potash are used in a large
Keywords 72 number of manufacturing processes. The chemicals are avail-
1.3 The values stated in SI units are to be regarded as able in several grades depending on their intended use. The test
standard. No other units of measurement are included in this methods listed in 1.2 provide procedures for analyzing caustic
standard with the exception of inch-pound units for apparatus soda and caustic potash to determine if they are suitable for
descriptions. their intended use.
1.4 Review the current Material Safety Data Sheet (MSDS) 4. Apparatus
for detailed information concerning toxicity, first-aid
procedures, handling, and safety precautions. 4.1 Photometers and Photometric Practice—Photometers
and photometric practice used in these test methods shall
1.5 This standard does not purport to address all of the conform to Practice E60.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 5. Reagents
priate safety and health practices and determine the applica- 5.1 Purity of Reagents—Unless otherwise indicated, it is
intended that all reagents shall conform to the specifications of

1 2
These test methods are under the jurisdiction of ASTM Committee E15 on For referenced ASTM standards, visit the ASTM website, [Link], or
Industrial and Specialty Chemicals and are the direct responsibility of Subcommit- contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
tee E15.01 on General Standards. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved April 1, 2009. Published April 2009. Originally the ASTM website.
3
approved in 1965. Last previous edition approved in 2004 as E291 – 04. DOI: The last approved version of this historical standard is referenced on
10.1520/E0291-09. [Link].

*A Summary of Changes section appears at the end of this standard

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 E291 − 09
the Committee on Analytical Reagents of the American Chemi- and liquid caustic potash. Liquid caustic potash at a concen-
cal Society, where such specifications are available.4 Other tration of 45 % remains liquid at temperatures down to − 29°C,
grades may be used, provided it is first ascertained that the and freezing or crystallization will only be encountered under
reagent is of sufficiently high purity to permit its use without severe cold weather. Caustic soda liquors are usually shipped
lessening the accuracy of the determination. in insulated tank cars at elevated temperatures, and minimum
5.2 Purity of Water—Unless otherwise indicated, references temperatures must be maintained if unloading and sampling
to water shall be understood to mean Type II or Type III problems are to be avoided. Viscosity increases near the
reagent water conforming to Specification D1193. freezing point and creates pumping problems. Even partial
freezing changes the composition of the remaining liquor and
6. Hazards causes sampling and analysis problems. Be sure contents are
completely liquid and well mixed before sampling. The fol-
6.1 Sodium and potassium hydroxides are caustic alkalies
lowing minimum temperatures should be maintained for proper
which, in their anhydrous or strong solution form, are hazard-
sampling of bulk shipments:
ous materials. In contact with the skin they produce burns
50 % NaOH liquor 20°C
which may be quite serious unless promptly treated. Their 53 % NaOH liquor 30°C
action is insidious since they produce no immediate stinging or 70 to 73 % NaOH liquor 71°C
burning sensation and damage may result before their presence 7.2 Sample Containers—The choice of container construc-
is realized. tion material is important for caustic liquor samples, especially
6.2 Eyes are particularly vulnerable to severe damage from for those to be taken or held at elevated temperatures. Glass
these alkalies. can be used except where silica is to be determined. Polyeth-
6.3 Laboratory workers handling these alkalies should use ylene or polypropylene containers which have high-
safety goggles or face shields and rubber gloves and avoid temperature properties may also be used. Nickel is the best
spillage on clothing. These materials rapidly attack wool and practical metal for a metallic sample container for caustic
leather. liquors. For the analysis of 73 % caustic soda, the entire sample
should be in the liquid state before removing any portion, and
6.4 Spilled caustic should be flushed away with water where such portions must then be used in their entirety to avoid the
possible, or covered with absorbent material (such as sawdust, factor of segregation on freezing. Caustic soda of 73 %
vermiculite, or baking soda) and swept up and discarded in concentration may also be “cast” into glass or plastic bottles or
accordance with all applicable federal, state, and local health tubes, or nickel or silver metallic molds. The molds are later
and environmental regulations. Last traces may be neutralized removed and the samples chipped or crushed for analysis. If
with dilute acetic acid and the area washed with water. this is done, the factors of segregation on freezing and
6.5 Perchloric acid is toxic, corrosive, and a strong oxidizer. atmospheric exposure while crushing must be borne in mind.
Laboratory workers handling this acid should use safety
7.3 Sampling Devices and Techniques:
goggles or face shields and rubber gloves.
7.3.1 Liquid Caustic—Simple “dipper” or “tap” samples
7. Sampling from large quantity shipments or tanks of caustic liquor are
inadequate for purchaser and vendor purposes. Numerous
7.1 General—The nature of the caustic alkalies is such as to specially designed devices are available to procure samples
require special care at all points of sampling and preparation from various levels in tanks. A useful type of such samplers for
for analysis. The following information is included in order small tanks has three or five containers mounted on a single rod
that representative samples may be ensured. Additional pre- so that when the device is lowered into a tank and the stoppers
cautions may be necessary if trace constituents, not covered in are pulled, samples are simultaneously taken at the different
these test methods, are to be determined. Instructions for such levels. These are then combined to provide a representative
procedures may be obtained from the publications of most average sample. Shipments should be sampled at least at the
major producers. Sampling techniques must be such as to limit upper, middle, and lower thirds. Samples should never be taken
or prevent atmospheric exposure since sodium and potassium at the surface of the liquid. If it is not necessary to analyze the
hydroxides, both as aqueous solutions and as anhydrous liquor before unloading, sampling may be accomplished by a
products, rapidly absorb moisture and carbon dioxide (and “continuous drip” from a small tap-off with the regulating
other acid gases) from the atmosphere. The aqueous solutions valve in a vertical section of the unloading line. The “drip” is
are corrosive and sampling devices and sample containers must so timed as to collect the desired amount of sample uniformly
be selected to avoid contamination with any constituent later to during the time of unloading.
be determined. Strong aqueous solutions of these alkalies are
7.3.2 Anhydrous Products:
available commercially under the names liquid caustic soda
[Link] Commercial anhydrous caustic soda or caustic pot-
ash is packaged in drums in solid, flake, ground, or powdered
4
Reagent Chemicals, American Chemical Society Specifications , American forms. Sampling and handling of these materials must be done
Chemical Society, Washington, DC. For suggestions on the testing of reagents not with minimum atmospheric exposure.
listed by the American Chemical Society, see Analar Standards for Laboratory
[Link] In the case of flake, ground, or powdered sodium or
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, potassium hydroxides, the top 75 or 100 mm of material in a
MD. drum should first be removed and a sample then taken from the

2
 E291 − 09
center part of the drum. The sample should be placed imme- solution to about 400 mL with water and cool to room
diately in a suitable wide-mouth container then closed and temperature. After cooling, dilute to 1 L and mix thoroughly.
sealed with taps or wax. 11.3 With a volumetric pipet, transfer 50 mL (see Note 1) of
[Link] Solid caustic shall be packaged by filling metal the prepared solution to a 500-mL Erlenmeyer flask and add 2
drums with molten anhydrous product and allowing drums and to 4 drops of modified methyl orange indicator solution (see
contents to cool before sealing air tight. On cooling and Note 2). Titrate this solution with standard 1.0 meq/mL acid to
solidifying, impurities present in the caustic tend to segregate a gray end point (see Note 3) and record the volume and
and concentrate in the bottom section. To sample such material temperature of acid used. Correct the acid meq/mL for any
properly, the metal drum must be opened at the vertical seam difference from the standardization temperature by use of the
and removed. The solid cake may then be sampled either by factor ∆N/°C = 0.00035 between 20 and 30°C adding the
drilling at representative levels with a 19-mm auger bit (may correction when temperature of use is below (subtracting when
cause metal contamination) or by splitting the cake in half above) the temperature of standardization. (See Practice E200.)
vertically with hammer and chisel and chiseling off represen-
tative small fragments so that the total sample represents a NOTE 1—If a 100-mL buret is to be used for this titration use a 100-mL
aliquot.
vertical cross section through the cake. In either case, the NOTE 2—If desired, methyl orange indicator solution may be used.
sample shall be promptly bottled and sealed in a wide-mouth NOTE 3—The analyst should attempt to end the titration at the same
container. In the laboratory, the lumps shall be reduced to shade of color as was used for the end point in the standardization of the
convenient size by enclosing in several thicknesses of clean acid.
cloth or kraft paper and pounding with a hammer. The crushed
12. Calculation
material shall be bottled and thoroughly mixed before analysis.
12.1 Calculate the total alkalinity as % sodium oxide or
TOTAL ALKALINITY potassium oxide as follows:
8. Scope A 3 B 3 0.030990
Sodium oxide, % mass 5 3 100 (1)
W
8.1 This test method covers the determination of the total
A 3 B 3 0.047102
alkalinity of 50 and 73 % liquid caustic soda, 45 % liquid Potassium oxide, % mass 5 3 100 (2)
W
caustic potash, and anhydrous caustic soda and caustic potash.
where:
9. Summary of Test Method A = acid required for titration of the sample, mL
9.1 Total alkalinity is determined by titration with standard B = corrected meq/mL of the acid, and
hydrochloric acid solution using methyl orange indicator W = mass of sample in the aliquot, g.
solution or modified methyl orange indicator solution. 12.2 Calculate the total alkalinity as the respective hydrox-
ide as follows:
10. Reagents
Sodium hydroxide, % mass 5 1.2907 3 %mass Na2 O (3)
10.1 Hydrochloric (or Sulfuric Acid), Special (1.0 meq/
mL)—Prepare in accordance with Practice E200. Potassium hydroxide, % mass 5 1.1912 3 %mass K 2 O (4)

10.2 Methyl Orange Indicator Solution—See Practice E200. 12.3 If actual hydroxide content is desired, the carbonate
content must be determined separately as described in Sections
10.3 Modified Methyl Orange Indicator Solution—See Prac- 15 – 24 or Sections 25 – 33. Then:
tice E200.
Sodium hydroxide ~ actual! , % mass 5 A 2 ~ B 3 0.755! (5)
10.4 Water, Distilled, carbon dioxide-free (freshly boiled
Potassium hydroxide ~ actual! , % mass 5 C 2 ~ D 3 0.812! (6)
and cooled).
where:
11. Procedure A = % mass NaOH (total alkali),
11.1 Transfer to a tared, covered weighing bottle a sample B = % mass Na2CO3,
of such size as determined from Table 1. C = % mass KOH (total alkali), and
D = % mass K2CO3.
11.2 Weigh the sample to the nearest 1 mg and transfer it to
a 1-L volumetric flask using several rinses of water to remove 13. Report
all traces of caustic from the weighing bottle. Dilute the
13.1 Report the % mass of sodium oxide or potassium oxide
to the nearest 0.01 %.
TABLE 1 Sample Size for Total Alkalinity
TABLE 2 Sample Size for Carbonate Analysis
Sample Sample Size, g
50 % NaOH 65 to 78 Percent Na2CO3 or Percent
Sample Size, g
73 % NaOH 45 to 52 K2CO3 Expected
Anhydrous NaOH 32 to 40 0.01 to 0.10 8 to 10
45 % KOH 100 to 120 0.10 to 0.50 5 to 7
Anhydrous KOH 48 to 60 0.50 to 1.00 2 to 4

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 E291 − 09
14. Precision and Bias 17.1.6 Tubing Assembly, D, as illustrated in Fig. 4.
14.1 The following criteria should be used in judging the 18. Reagents
acceptability of results (Note 4):
14.1.1 Repeatability (Single Analyst)—The standard devia- 18.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
tion for a single determination has been estimated to be chloric acid (HCl).
0.057 % absolute at 144 DF. The 95 % limit for the difference 18.2 Methyl Orange Indicator Solution (1 g/L)—See Prac-
between two such runs is 0.16 % absolute. tice E200.
14.1.2 Laboratory Precision (Within-Laboratory, Between- 18.3 Potassium Hydroxide (35 % Solution)—Dissolve 350 g
Days Variability)—The standard deviation of results (each the of potassium hydroxide (KOH) in 650 mL of water.
average of duplicates), obtained by the same analyst on
different days, has been estimated to be 0.17 % absolute at 72 18.4 Sodium Carbonate (Na2CO3), anhydrous.
df. The 95 % limit for the difference between two such 18.5 Water, Distilled, carbon dioxide-free (freshly boiled
averages is 0.48 % absolute. and cooled).
14.1.3 Reproducibility (Multilaboratory)—The standard de-
viation of results (each the average of duplicates), obtained by 19. Preparation of Apparatus
analysts in different laboratories, has been estimated to be 19.1 Assemble the apparatus as shown in Fig. 1 after
0.25 % absolute at 10 df. The 95 % limit for the difference preparing the various parts as follows:
between two such averages is 0.70 % absolute. 19.1.1 Compensator Tube, C—Warm the bulb slightly and
NOTE 4—These precision estimates are based on an interlaboratory place two or three drops of water in the tube. Then add
study on five samples comprising 45 % KOH, 50 % NaOH, 73 % NaOH, sufficient mercury so that when the tube is at room temperature
anhydrous NaOH, and anhydrous KOH. The number of laboratories and normal atmospheric pressure the mercury columns are
analyzing each sample ranged from seven to fifteen with one analyst in approximately level and are about 11⁄2 to 2 in. (38 to 51 mm)
each performing duplicate determinations and repeating one day later.5
Practice E180 was used in developing these precision estimates.
in length. This is a trial and error operation. Manipulation by
alternately warming and cooling the bulb is helpful in making
14.2 Bias—The bias of this test method has not been this adjustment.
determined because of the unavailability of suitable reference 19.1.2 Absorption Pipet, K—Fill this pipet with sufficient
materials. caustic potash solution to fill the left bulb completely and to
have about 1-in. (25-mm) depth in the right bulb. Protect the
SODIUM CARBONATE OR POTASSIUM solution from the atmosphere with a gas expansion bag, K2.
CARBONATE (GAS-VOLUMETRIC TEST METHOD) 19.1.3 Glass Water Jacket, O—Bore suitable holes in two
No. 12 rubber stoppers, as shown in Fig. 1, to support the buret
15. Scope and compensator tube. An additional hole in the top stopper
will permit easy filling with water.
15.1 This test method describes the gas-volumetric determi-
19.1.4 Use a ring stand about 30 in. (760 mm) high with a
nation of sodium carbonate or potassium carbonate in caustic
heavy base to mount the various parts of the apparatus with
soda or caustic potash respectively. The lower limit of deter-
suitable clamps. Arrange the parts so that glass tube connec-
mination is 0.001 g as carbon dioxide.
tions are as close as possible and held with the rubber or plastic
16. Summary of Test Method tubing connectors, F.
19.1.5 Aspirator Bottle, J—Fill with a 20 % solution of
16.1 Carbon dioxide is evolved by acid decomposition of sodium chloride (NaCl) or calcium chloride (CaCl2), acidify
carbonate in the sample. The volume of CO2 is measured and slightly, and add a few drops of methyl red indicator solution
calculated as sodium carbonate or potassium carbonate. to color the solution. Distilled water may be used in place of
the salt solution.
17. Apparatus
17.1 Carbon Dioxide Evolution, Measurement, and Absorp- 20. Calibration of Apparatus (Machine Factor)
tion Device, as illustrated in Fig. 1 and consisting of the 20.1 The factor may be determined theoretically, but is done
following special parts: more conveniently by a series of actual tests on a sample of
17.1.1 Aspirator Bottle, J, 500-mL, used for leveling. known carbon dioxide content. Weigh 2.000 g of anhydrous
17.1.2 Compensator Tube, C, as shown in Fig. 1 and Na2CO3, dissolve in 25 mL of water, dilute to 100 mL in a
conforming to details shown in Fig. 2. volumetric flask at room temperature, and mix thoroughly.
17.1.3 Gas Buret, B, 100-mL, modified as shown in Fig. 3. Using 10-mL aliquot portions of this, measured by means of
17.1.4 Gas Pipet, K, preferably of the bubbler type. volumetric pipet, determine the amount of carbon dioxide
17.1.5 Glass Condenser with Jacket, L, 12 in. (305 mm) (CO2) it contains by the evolution method as described in
long and 11⁄4 in. (32 mm) in outside diameter. The condenser Section 21. At least five determinations should be made and the
tube shall be of 8-mm outside diameter glass tubing. results averaged. The machine factor (F) is calculated as
follows:
5
Supporting data have been filed at ASTM International headquarters and may 0.2000 3 0.41523
F5 (7)
be obtained by requesting Research Report No. E15-1040. A

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 E291 − 09

A— Water above mercury column of manometer. I— Three-way stop cock with TFE-fluorocarbon plug.
B— Gas buret, Fig. 3. J— Aspirator bottle.
C— Compensator tube, Fig. 2. K— Absorption pipet for KOH solution.
D— Capillary glass tubing with small bubble at D1, Fig. 4. K1— Gas expansion bag.
E— Filling funnel. L— Glass condenser.
F— Heavy rubberor plastic connectors. M— Rubber stopper.
G— Rubber tubing about 91 cm long. N— Sample receptacles.
H1, H2, H— Two way glass stop cock. O— Glass water jackets, 63.5 mm in diameter.

FIG. 1 Carbon Dioxide Evolution, Measurement, and Absorption Device

where: 21.2.2 With stopcock H open, turn stopcock H1 to the open

A = CO2 found, mL. position, level the mercury columns by manipulation of level-
ing bottle J and close H1.
21. Procedure 21.2.3 Now open stopcock I to connect B with the tube
21.1 Have sample flask N clean and dry. Stopper the flask leading to N, fill the buret and tube with the retaining solution
with a rubber stopper or cork and weigh to the nearest 0.01 g. by raising J, and close H when the condenser tube is filled.
Transfer the following approximate mass of caustic to the flask, 21.2.4 Open stopcock H2 and rinse the funnel E and stopper
replace the stopper and reweigh to the nearest 0.01 g. After with water.
weighing, add a small piece of iron wire about the size of a
pinhead, 1 drop of methyl orange indicator solution, and water 21.3 Connect N to the apparatus and close stopcock H2. Into
until flask N is about three quarters full. Replace the stopper. E pour an amount of concentrated HCl slightly more than
enough to neutralize the sample. Now open stopcock H and
21.2 Before connecting N to the apparatus, make the fol- then H2 sufficiently to let the acid drop slowly into N until the
lowing adjustments: solution is acid, and close H2.
21.2.1 Check the level of the potash solution in K with
relation to stopcock I. The potash liquor should fill the entrance 21.4 Fill E nearly full with water, heat the contents of N to
tube up to a previously marked point approximately 1 cm boiling, and continue boiling very gently for at least 2 min.
below stopcock I. If such is not the case, close H1, open H, turn Remove the burner, open stopcock H2 and lower J (if neces-
I to connect J with K, and lower J to bring the level of the sary) until the water from E fills N and the connecting tube just
potash up to the previously marked point. Turn three-way up to I. Give three-way cock I one-quarter turn to cut off all
stopcock I one-quarter turn to close all openings. openings.

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 E291 − 09

FIG. 4 Tubing Assembly

FIG. 2 Compensator Tube

21.5 Raise J until its liquid level is approximately the same
as the water in the buret, open H1, and raise or lower J until the
mercury columns in the compensator are level; then close H
and H1 and read the buret. Record this buret reading as A.
21.6 Holding J slightly above the liquid level in B, open H
and turn I to connect with the absorption pipet K. Raise
leveling bottle J to force the gas into potash pipet K until the
liquid in B reaches a height approximately equivalent to that of
Stopcock I. At this point lower J to return the gas to buret B and
bring the potash level up to the previously marked point. This
procedure should be repeated at least twice more to absorb the
carbon dioxide completely. After three passes into K, bring the
potash liquor level up to the previously marked point and turn
I one-quarter turn. Hold J at the approximate water level of B,
open H1, level the mercury columns as before, and close H and
H1 and read the buret. Record this buret reading as B.
21.7 The difference (A − B), represents the millilitres of
CO2 evolved and absorbed. This difference, multiplied by a
machine factor, gives the mass of CO2 in the sample.
22. Calculation
22.1 Calculate the % mass solution carbonate or potassium
carbonate present as follows:
~ A 2 B ! 3 F 3 2.4083
Sodium carbonate, % mass 5 3 100 (8)
W
~ A 2 B ! 3 F 3 3.1405
Potassium carbonate, % mas s 5 3 100 (9)
NOTE 1—Dimensions of tubing diameters are approximate. W
FIG. 3 Gas Buret where:
A = buret reading before KOH addition,

6
 E291 − 09

B = buret reading after KOH addition, 26. Summary of Test Method

F = machine factor, and 26.1 Carbon dioxide is evolved by acid decomposition of
W = sample used, g. the carbonate in the sample and is absorbed on sodium
23. Report hydrate-asbestos absorbent. The increase in mass is a measure
of the carbonate present.
23.1 Report the % mass of sodium carbonate or potassium
carbonate to the nearest 0.01 %. 27. Apparatus
24. Precision and Bias 27.1 Fig. 5 illustrates the analytical train required. The
24.1 The following criteria should be used for judging the principal parts are as follows:
acceptability of results (see Note 5): 27.1.1 Separatory Funnel, C, 100-mL capacity.
24.1.1 Repeatability (Single Analyst)—The standard devia- 27.1.2 Flask, F, 250-mL extraction.
tion for a single determination has been estimated to be the 27.1.3 Condenser, G, 8-in. (203-mm) modified Liebig.
value given in Table 3 at the indicated degrees of freedom. The 27.1.4 Drying Tubes, H and J, Schwartz, glass-stoppered, 6
95 % limit for the difference between two such runs is also in. (152 mm).
given in Table 3. 27.1.5 Drying Tubes, L, N, O, P, Schwartz, glass-stoppered,
24.1.2 Laboratory Precision (Within-Laboratory, Between- 4 in. (101.6 mm).
Days Variability)—The standard deviation of results (each the 27.1.6 Bubbler Bottle, Q, 4-oz (0.056-L) capacity.
average of duplicates), obtained by the same analyst on 27.1.7 Siphon-Vacuum Bottle, 1-gal (3.6-L) capacity.
different days, has been estimated to be the value given in
28. Reagents
Table 3 at the indicated degrees of freedom. The 95 % limit for
the difference between two such averages is also given in Table 28.1 Barium Perchlorate (or Magnesium Perchlorate),
3. anhydrous, granular.
24.1.3 Reproducibility (Multilaboratory)—The standard de- 28.2 Perchloric Acid (1 + 2)—Mix 1 volume of 60 % per-
viation of results (each the average of duplicates), obtained by chloric acid (HClO4) with 2 volumes of water and boil for 10
analysts in different laboratories, has been estimated to be the min in a large Erlenmeyer flask. Cool and bottle.
value given in Table 3 at the indicated degrees of freedom. The
28.3 Silver Arsenite in Sulfuric Acid—Dissolve 2 g of
95 % limit for the difference between two such averages is also
pulverized arsenious oxide (As2O3) in the least amount of
given in Table 3.
potassium hydroxide (KOH) solution (100 g/L) that will effect
NOTE 5—These precision estimates are based on an interlaboratory solution. Dilute to 250 mL and add dilute sulfuric acid (H2SO4,
study on six samples with carbonate contents as follows: 1 + 9) until neutral to litmus. Add silver nitrate (AgNO3)
Approximate solution (50 g/L) as long as a yellow precipitate forms, keeping
Percentage of
Sample Carbonate
the solution neutral by dropwise addition of KOH (100 g/L)
45 % KOH 0.01 solution when necessary. Stir until coagulated, settle, and wash
50 % NaOH 0.20, 0.05, 0.13 by decantation. Dissolve the precipitate in an excess of H2SO4
73 % NaOH 0.08
Anhydrous NaOH 0.35 (1 + 9), dilute to 150 mL, and filter out any precipitated silver
chloride (AgCl).
One analyst in each of fourteen laboratories performed duplicate
determinations and repeated one day later.5 Practice E180 was used in 28.4 Sodium Hydrate—Asbestos Absorbent, 12 to 20 mesh.
developing these precision estimates.
28.5 Zinc Metal, clean, mossy.
24.2 Bias—The bias of this test method has not been
determined because of the unavailability of suitable reference 29. Preparation of Apparatus
materials.
29.1 The apparatus shall be assembled as shown in Fig. 5
and should conform to the description given. It shall consist of
SODIUM CARBONATE OR POTASSIUM a 250-mL extraction flask F in which the CO2 is evolved. Acid
CARBONATE (GRAVIMETRIC TEST METHOD) is admitted through the stopcock D from separatory funnel C
which should be of at least 80-mL capacity. The acid delivery
25. Scope tube entering F should be bent upwards at the end to prevent
25.1 This test method covers the gravimetric determination the escape of CO2. To the top of C shall be attached a similar
of carbonate in caustic soda or caustic potash. The lower limit tube B containing sodium hydrate-asbestos absorbent protected
of determination is 0.001 g as carbon dioxide. by glass wool, to purify the carrier air which enters at stopcock

TABLE 3 Precision for Carbonate (Gas-Volumetric Method)

Repeatability Laboratory Precision Reproducibility
Standard Degrees of 95 % Range, Standard Degrees of 95 % Range, Standard Degrees of 95 % Range,
Level %
Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute
0.01–0.02 0.0034 24 0.01 0.0062 13 0.02 0.0093 5 0.03
0.04–0.08 0.0069 28 0.02 0.0145 14 0.04 0.021 6 0.06
0.12–0.35 0.017 28 0.05 0.019 14 0.05 0.034 6 0.10

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 E291 − 09

FIG. 5 Analytical Train

A. The flask shall be heated directly by a bunsen burner and can be closed by pinchcock S and the rapidity of emptying
shall be protected from drafts by shield E, either of metal or regulated by screw clamp U.
asbestos. The gases escape from F through an 8-in. (203-mm) 29.6 A freshly prepared train should be conditioned with a
water-cooled condenser G. All of this part of the apparatus 0.2-g sample of Na2CO3 carried through the analysis to
shall be conveniently mounted on one large ring stand, saturate the reagents with CO2. Before the train is ready for a
facilities being arranged for removing the flask F and guard series of determinations, successive weighings of the tube N
tube B for each determination. All stoppers and joints must be must agree within 0.0002 g before and after the passage of one
absolutely airtight. half of the volume of air represented by the capacity of R, when
29.2 The U-tubes shall be hung individually from hooks by no sample is in place. Tube O shall be used as a precautionary
copper wire loops securely fastened to the necks of the tubes. measure. At the indicated gas flow, N will be found to absorb
H is a 6-in. (152-mm) U-tube containing glass beads and a all the CO2 until its capacity is nearly depleted. Tube O should
solution of silver arsenite Ag3AsO3 in dilute H2SO4. Its always be weighed as a check for any CO2 not absorbed in N.
function is to remove alkali gases, sulfides, chlorides, chlorine,
and other oxidizing gases. I is a plug of glass wool to retain any 30. Procedure
reagent entrained in the gas. J is a 6-in. U-tube containing 30.1 Weigh into a tared evolution flask F to the nearest 0.1
H2SO4 and glass beads to absorb most of the water from the g, a sample of size determined from Table 4. Connect the flask
gas. It is also protected by a plug of glass wool I in the outlet F to the analytical train as shown in Fig. 5.
tube. K is a bulb containing clean mossy zinc which serves to 30.2 Open all stopcocks and adjust screw clamp U for a
catch any trace of acid carried over from J. L is a 4-in. flow of 60 to 80 mL/min corresponding to 3 to 4 bubbles/s
(102-mm) U-tube containing anhydrous barium perchlorate when the bubbler Q is built as described in 29.4. Close
(Ba(ClO4)2) or anhydrous magnesium perchlorate (Mg- stopcock D and pinchcock S. Remove B and add at least 75 mL
(ClO4)2). The tube shall be prepared in three sections separated of the diluted HClO4 into C and replace tube B. Open
by glass wool to eliminate channeling by the gases. pinchcock S and then stopcock D carefully to admit the acid.
29.3 N and O are 4-in. U-tubes for the absorption and When all the acid has entered, begin heating with a 25-mm
weighing of the CO2, each prepared with two sections of bunsen flame. When the heating has progressed to the point
sodium hydrate-asbestos absorbent and one of anhydrous where the flow of air through the acid delivery tube seems to
Ba(ClO4)2 or anhydrous Mg(ClO4)2 separated by glass wool, stop and the liquid shows a tendency to back up in the tube,
the desiccant being nearest the outlet end. These tubes shall be close D.
connected to the system and each other by the short glass tubes 30.3 After 5 min of brisk boiling, remove the flame, open
M, and the tubes shall be disconnected and weighed with their stopcock D, and continue drawing air through the train until the
rubber tubing connections attached. water in bottle R has been siphoned off almost entirely. Close
29.4 P is a 4-in. U-tube filled with desiccant to prevent any S, the last stopcock in P, both stopcocks in O and in N, the last
accidental back draft from containing any weighable moisture. stopcock in L, and the first stopcock in H.
Q is a bubbler bottle containing concentrated H2SO4. If the
bubbler tube is of 6-mm bore and the tip is placed 1.9 cm TABLE 4 Sample Size for Carbonate Analysis
below the surface of the acid, one bubble per second will Percent Na2CO3 or Percent Sample
indicate about 20-mL/min gas flow. K2CO3 Expected Size, g

29.5 R is a 1-gal (3.6-L) siphon vacuum bottle. It provides 0.01 to 0.10 15 to 20

0.10 to 0.50 10 to 15
sufficient vacuum for the flow required, and its capacity is a 0.50 to 1.00 7 to 10
good measure of the time required for an analysis. The siphon

8
 E291 − 09
30.4 Remove N and O and allow to stand in the balance case Approximate
for at least 10 min. Open the stopcocks momentarily to attain Percentage of
Sample Carbonate
atmospheric pressure, wipe gently with tissue, and weigh 45 % KOH 0.01
accurately to 0.1 mg. 50 % NaOH 0.02, 0.05, 0.13
73 % NaOH 0.10
Anhydrous NaOH 0.41
31. Calculation
One analyst in each of twelve laboratories performed duplicate deter-
31.1 Calculate the percent sodium carbonate or potassium minations and repeated one day later.5 Practice E180 was used in
carbonate as follows: developing these precision estimates.
A 3 2.4083 33.2 Bias—The bias of this test method has not been
Sodium carbonate, % mass 5 3 100 (10)
W determined because of the unavailability of suitable reference
A 3 3.1405 materials.
Potassium carbonate, % mass 5 3 100 (11)
W CHLORIDE, TITRIMETRIC
where:
34. Scope
A = total grams increase in the mass of U-tubes O and N,
and 34.1 This test method covers the volumetric determination
W = sample used, g. of chloride in caustic soda or caustic potash by the Volhard test
method. The lower limit of determination is 0.001 g as
32. Report chloride.
32.1 Report the % mass of sodium carbonate or potassium 35. Summary of Test Method
carbonate to the nearest 0.01 %.
35.1 The sample is diluted, acidified, and treated with a
small excess of standard silver nitrate solution. The precipi-
33. Precision and Bias tated silver chloride is removed by filtration and the excess
33.1 The following criteria should be used for judging the silver nitrate is titrated with standard ammonium thiocyanate
acceptability of results (see Note 6): solution using ferric ammonium sulfate indicator.
33.1.1 Repeatability (Single Analyst)—The standard devia-
36. Reagents
tion for a single determination has been estimated to be the
value given in Table 5 at the indicated degrees of freedom. The 36.1 Ammonium Thiocyanate, Standard Solution (0.1 meq/
95 % limit for the difference between two such runs is also mL)—See Practice E200.
given in Table 5. 36.2 Ferric Ammonium Sulfate Indicator Solution—See
33.1.2 Laboratory Precision (Within-Laboratory, Between- Practice E200.
Days Variability)—The standard deviation of results (each the 36.3 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
average of duplicates), obtained by the same analyst on (HNO3).
different days, has been estimated to be the value given in
Table 5 at the indicated degrees of freedom. The 95 % limit for 36.4 Silver Nitrate, Standard Solution (0.1 meq/mL)—See
the difference between two such averages is also given in Table Practice E200.
5.
37. Procedure
33.1.3 Reproducibility (Multilaboratory)—The standard de-
viation of results (each the average of duplicates), obtained by 37.1 If the approximate chloride content of the sample is
analysts in different laboratories, has been estimated to be the known, take a sample of size as indicated in Table 6.
value given in Table 5 at the indicated degrees of freedom. The 37.2 If the approximate chloride content is unknown, make
95 % limit for the difference between two such averages is also a trial determination with a sample of 10 g. If necessary, repeat
given in Table 5. with a proper size sample for the actual determination.
NOTE 6—These precision estimates are based on an interlaboratory 37.3 Weigh the sample, in a tared and covered weighing
study on six samples with carbonate contents as follows: bottle, to the nearest 0.001 g for smaller samples (nearest 0.01

TABLE 5 Precision for Carbonate (Gravimetric Method)

Repeatability Laboratory Precision Reproducibility
Standard Degrees of 95 % Range, Standard Degrees of 95 % Range, Standard Degrees of 95 % Range,
Level, %
Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute Deviation Freedom Percent Absolute
0.01–0.02 0.0034 20 0.01 0.0025 10 0.01 0.0054 4 0.02
0.04–0.08 0.0068 20 0.02 0.0058 11 0.02 0.0018 5 0.05
0.12–0.15 0.0095 10 0.03 0.014 6 0.04 0.031 5 0.09
Apprx. 0.40 0.016 10 0.04 0.025 5 0.07 0.043 4 0.12

9
 E291 − 09
TABLE 6 Sample Size for Chloride Analysis 40.1.2 Laboratory Precision (Within-Laboratory, Between-
Percent NaCl or Percent Sample Days Variability)—The standard deviation of results (each the
KCl Expected Size, g average of duplicates), obtained by the same analyst on
1 to 2 5 different days, has been estimated to be 0.0036 % absolute at
0.5 to 0.9 10
0.01 to 0.49 20 28 df. The 95 % limit for the difference between two such
averages is 0.01 % absolute.
40.1.3 Reproducibility (Multilaboratory)—The standard de-
viation of results (each the average of duplicates), obtained by
g for larger samples). Transfer the sample quantitatively to a analysts in different laboratories, has been estimated to be
500-mL Erlenmeyer flask using about 100 mL of water to 0.0069 % absolute at 6 df. The 95 % limit for the difference
effect transfer and solution. Add 1 mL of ferric indicator and between two such averages is 0.02 % absolute
(slowly) sufficient HNO3 (sp gr 1.42) to dissolve the reddish- NOTE 8—These precision estimates are based on an interlaboratory
brown precipitate formed with the ferric indicator. Cool to study on four samples covering the range from 0.15 to 0.8 % chloride in
room temperature. Add 0.1 meq/mL AgNO3 solution (Note 7) potassium hydroxide and sodium hydroxide. One analyst in each of seven
laboratories performed duplicate determinations and repeated one day
in an excess of 5 to 10 mL over that required to react with the later.5 Practice E180 was used in developing these precision estimates.
chloride, agitating continuously while adding. The total
amount added will depend on the average chloride content of 40.2 Bias—The bias of this test method has not been
the particular grade of caustic being analyzed. determined because of the unavailability of suitable reference
materials.
37.4 Filter off the precipitated silver chloride using semi-
quantitative paper and only one 5-mL portion of wash water. CHLORIDE, POTENTIOMETRIC TITRATION
Leave the filtrate in the receiver flask and back-titrate the
41. Scope
excess AgNO3 with 0.1 meq/mL NH4SCN solution to the first
reddish-brown color lasting for a minimum of 15 s. Record the 41.1 This test method was developed for the analysis of
volumes of titrants used to the nearest 0.02 mL. chloride in caustic soda and caustic potash. It covers the
potentiometric titration of 0.3 to 1.2 % of chloride in caustic
NOTE 7—It is sometimes preferred to add 0.5 to 1.0 mL of 0.1 meq/mL
NH4SCN solution before adding AgNO3 which is then added in an amount soda and caustic potash. This test method may be applied to
2 to 5 mL in excess of that required to cause the disappearance of the other concentrations by using equivalent sample weights.
brown color. Any NH4SCN so added must be included in the calculation.
The sample is then back-titrated in accordance with 37.4. 42. Summary of Test Method
42.1 Chloride is determined by potentiometric titration with
38. Calculation 0.1 meq/mL silver nitrate in conjunction with a silver billet
38.1 Calculate the % mass of chloride as follows: combination electrode. An automatic titrator or a pH meter in
the millivolt mode may be used to obtain the potentiometric
@ ~ A 3 N 1 ! 2 ~ B 3 N 2 ! # 3 0.035453
Chloride, % mass 5 3 100 titration end point.
W
(12) 43. Apparatus
where: 43.1 Automatic Titrator or pH Meter, switched to millivolt
A = AgNO3 solution added, mL, mode.
B = NH4SCN solution added, total mL, 43.2 Buret, 20-mL automatic delivery type or 25-mL
N1 = meq/mL of AgNO3 solution used, manual type.
N2 = meq/mL of NH4SCN solution used, and
W = sample used, g. 43.3 Silver Billet, combination electrode.

38.2 Calculate the % mass of sodium chloride or potassium 43.4 Magnetic Stirrer and Stir Bars.
chloride, if desired, as follows: 44. Reagents
Sodium chloride, % mass 5 chloride, wt % 3 1.6485 (13) 44.1 Nitric Acid (sp gr 1.42)—concentrated nitric acid
Potassium chloride, % mass 5 chloride, wt % 3 2.1029 (14) (HNO3).
44.2 Phenolphthalein Indicator Solution (10 g/L)—
39. Report Dissolve 1 g of phenolphthalein in 100 mL of ethanol (95 %)
39.1 Report the % mass of chloride to the nearest 0.01 %. as prescribed in Practice E200.
44.3 Silver Nitrate, Standard Solution (0.1 meq/mL)—
40. Precision and Bias
Prepare in accordance with Practice E200, but standardize
40.1 The following criteria should be used for judging the using the potential (end point) break obtained using an auto-
acceptability of results (Note 8): matic titrator or pH meter in the millivolt mode.
40.1.1 Repeatability (Single Analyst)—The standard devia-
tion for a single determination has been estimated to be 45. Procedure
0.0071 % absolute at 56 df. The 95 % limit for the difference 45.1 For NaOH liquors, NaCl may drop out of solution and
between two such runs is 0.02 % absolute. must be redissolved prior to analysis. Whether NaCl crystals

10
 E291 − 09
are visible to the eye or not, place a magnetic stir bar in the 48.1.2 Laboratory Precision (Within-Laboratory, Between-
NaOH sample bottle and place the bottle on a magnetic Days)—Because all data were obtained on a single day, no
stirrer/heater. Loosen, but do not remove the cap on the sample estimate of laboratory precision is possible.
bottle. Adjust the heater setting to a very low position to allow 48.1.3 Reproducibility (Multilaboratory)—The standard de-
heating of the sample to only 25°C. Adjust the stirring rate to viation of single results obtained by analysts in different
give a visible vortex. Allow the sample to stir continuously for laboratories has been estimated to be 0.0293 % absolute at 5 df.
1 h. Then tighten the cap and allow the sample to cool to room The 95 % limit for the difference between two such results is
temperature before analysis. After cooling, invert the sample 0.08 % absolute.
bottle several times immediately before withdrawing the NOTE 9—These precision estimates are based on an interlaboratory
sample. study conducted in 1988–1989 on 50 % sodium hydroxide in which eight
45.2 Weigh 10 g of sample to the nearest 0.01 g into a laboratories ran triplicate determinations on one day on one sample
containing approximately 1 % sodium chloride. A one-way analysis of
250-mL beaker containing a stir bar. Carefully dilute to about variance was used in developing the precision estimates.5 The terms
100 mL with water, add 2 drops phenolphthalein, place the repeatability, reproducibility, and 95 % limits are used as defined in
beaker on the magnetic stirrer, and mix. Neutralize with Practice E180. The test method is believed applicable to potassium
concentrated nitric acid and add 2 to 10 drops in excess. The hydroxide, but the precision of this application has not been determined.
beaker contents must be cooled during the neutralization step 48.2 Bias—The bias of this test method has not been
to prevent violent spattering of the sample. Cover the beaker determined because of the unavailability of suitable reference
with a watchglass and cool the solution to ambient tempera- materials.
ture. Titrate the chloride in the sample with 0.1 meq/mL
AgNO3 using a 20-mL buret and following the automatic CHLORIDE, ION SELECTIVE ELECTRODE
titrator manufacturer’s instructions for titration and end point
49. Scope
determinations. Perform a “blank” titration on the same vol-
ume of HNO3 used for acidification of the sample added to the 49.1 This test method was developed for the analysis of
100 mL of water. chloride in caustic soda and caustic potash. It covers the ion
selective electrode determination of 1 to 120 µg/g chloride in
45.3 For manual titrations, in conjunction with a pH meter
caustic soda and caustic potash. This test method may be
in the millivolt mode, incremental additions of 0.1 meq/mL
applied to other concentrations by using equivalent sample
AgNO3 are made with corresponding millivolt readings re-
weights.
corded after each addition. Construct a potentiometric titration
curve by plotting millilitres of AgNO3 vs millivolts on linear 50. Summary of Test Method
graph paper and locate the inflection break point corresponding
to the end point volume. 50.1 The sample is acidified, followed by immersion of a
chloride ion selective electrode into the sample solution and
46. Calculation measurement of the millivolt response. Comparison of the
response to a standard calibration curve allows interpolation of
46.1 Calculate the % mass of chloride as follows: chloride amount.
~ A 2 B ! 3 N 3 0.035453
Chloride, % mass 5 3 100 (15) 51. Apparatus
W

where: 51.1 Expanded Scale pH meter, capable of reading to 0.1

mV or equivalent meter.
A = AgNO3 solution required for sample, mL,
B = AgNO3 solution required for blank, mL, 51.2 Solid-state Chloride Ion Selective Electrode.
N = meq/mL of AgNO3 solution used, and 51.3 Double-junction Reference Electrode.
W = sample used, g.
51.4 Magnetic Stirrer and Stir Bars—Affix styrofoam, ap-
46.2 Calculate the % mass of sodium chloride, if desired, as proximately 1⁄2 in. in size, to the stirrer surface to prevent heat
follows: transfer from the stirrer to the test solution in the beaker.
Sodium chloride, % mass 5 Chloride, wt % 3 1.6485 (16) Electrode readings are somewhat temperature dependent.

47. Report 52. Reagents

47.1 Report the % mass of chloride or sodium chloride to 52.1 Nitric Acid (5.0 meq/mL)—Using a graduated
the nearest 0.01 %. cylinder, slowly add 319 mL of concentrated HNO3 to a 1–L
volumetric flask which is approximately half-filled with water.
48. Precision and Bias Swirl the contents while adding HNO3. Dilute the contents of
48.1 The following criteria should be used for judging the the flask to the mark with water and mix well.
acceptability of results (Note 9): 52.2 Sodium Chloride, Standard Stock Solution (1000 mg/
48.1.1 Repeatability (Single Analyst)—The standard devia- L)—Dry NaCl at 105°C for 2 h. Weigh 1.000 g of the dried
tion of a single result has been estimated to be 0.00584 % NaCl and transfer to a 1–L volumetric flask half-filled with
absolute at 12 df. The 95 % limit for the difference between water. Swirl the contents thoroughly. Then dilute to the mark
two such results is 0.02 % absolute. with water and mix well.

11
 E291 − 09
52.3 Sodium Chloride Standard Solution (20 mg/L)—Pipet W = sample used, g.
20 mL of the 1000-mg/L stock solution (see 52.2) into a 1–L
55.2 Calculate the µg/g sodium chloride, if desired, as
volumetric flask and dilute to the mark with water. Mix well.
follows:
52.4 Ionic Strength Adjuster (ISA), 5 mol/L Sodium
sodium chloride, µg/g 5 chloride, ppm 3 1.6485 (18)
Nitrate—Weigh 425 g NaNO3, transfer to a 1–L volumetric
flask, and dilute to the mark with water and mix well. 56. Report
53. Preparation of Calibration Curve 56.1 Report chloride or sodium chloride to the nearest 1
µg/g.
53.1 To each of six 100-mL volumetric flasks, pipet 25 mL
of ISA and 10 mL of 5 meq/mL HNO3. Swirl contents of each 57. Precision and Bias
flask. Then pipet 4, 6, 8, 10, 15, and 20 mL of the 20-mg/L 57.1 The following criteria should be used in judging the
NaCl standard solution successively into the six volumetric acceptability of results (Note 10):
flasks. These six flasks are working standards containing 80, 57.1.1 Repeatability (Single Analyst)—The standard devia-
120, 160, 200, 300, and 400 µg NaCl, respectively. Dilute the tion of a single result has been estimated to be 1.02 µg/g NaCl
contents of each flask to the mark with water and mix well. at 18 df. The 95 % limit for the difference between two such
Beginning with the most dilute standard, successively transfer results is 3 µg/g NaCl.
the contents of each flask to a 150-mL beaker containing a 57.1.2 Laboratory Precision (Within-Laboratory, Between-
magnetic stir bar. Place the beaker on a magnetic stirrer. Days Variation)—Because all the data were obtained on a
53.2 Immerse the chloride and reference electrodes. Stir for single day, no estimate of laboratory precision is available.
4 min before recording a millivolt reading. After each standard 57.1.3 Reproducibility (Multilaboratory)—The standard de-
solution measurement, rinse both electrodes well with water viation of a single result obtained by analysts in different
and blot electrodes dry using absorbent paper. Using semilog laboratories has been estimated to be 5.18 µg/g sodium
graph paper, plot the millivolt reading for the 4-mL NaCl chloride at 8 df. The 95 % limit for the difference between two
standard on the linear axis versus 80 µg NaCl on the log axis. such results is 15 µg/g sodium chloride.
Similarly, plot millivolt readings for the other working stan-
NOTE 10—These precision estimates are based on an interlaboratory
dards (see 53.1) versus their micrograms of NaCl. For plotting study conducted in 1988–1989 on 50 % sodium hydroxide in which nine
the calibration curve, semilog paper having 2 cycles, 10 laboratories ran triplicate determinations on the same day on one sample
divisions per inch is recommended. containing approximately 34 µg/g sodium chloride. A one-way analysis of
variance was used to estimate the precision of the method.5 The terms
54. Procedure repeatability, reproducibility, and 95 % limits are used as defined in
Practice E180. This test method is believed applicable to potassium
54.1 For NaOH liquors, to ensure a homogeneous sample, hydroxide, but the precision of this application has not been determined.
invert the sample bottle several times prior to withdrawing a
57.2 Bias—The bias of this test method has not been
portion for analysis. Weigh 10 g of the sample to the nearest
determined because of the unavailability of suitable reference
0.01 g into a 100-mL volumetric flask. Add 40 mL of water
materials.
using a graduated cylinder and swirl the contents to mix.
54.2 Pipet 35 mL of 5 meq/mL HNO3 into the flask and IRON
swirl the contents. Allow the contents to come to room 58. Scope
temperature before dilution to the mark with water and final
mixing. 58.1 This test method covers the photometric determination
of iron in caustic soda or caustic potash. The lower limit of
54.3 Transfer the contents of the flask to a 150-mL beaker determination is 0.1 µg/g as iron.
containing a magnetic stir bar. Immerse the chloride and
reference electrodes and stir for 4 min before recording the 59. Summary of Test Method
millivolt reading. For replicate analyses, rinse electrodes well 59.1 Iron is reduced to the ferrous condition where it forms
and blot electrodes dry in between sample measurements. an orange-red complex with 1,10-phenanthroline (o-
54.4 Interpolate the µg NaCl value directly from the cali- phenanthroline) in an acetate-buffered solution at pH 5. Inten-
bration curve in accordance with Section 53. sity of the color so formed is measured at 510 nm in a
photometer calibrated with standard iron solutions. The color
55. Calculation develops within 15 min, is very stable, and follows Beer’s law.
55.1 Calculate the µg/g chloride as follows:
60. Interferences
C 3 0.60652
chloride, µg/g 5
W
(17) 60.1 Impurities normally found in caustic soda or caustic
potash do not cause any interference. Copper, if present to the
extent of 0.5 mg/100 mL of final solution, changes the hue of
the solution, but interferes only slightly when excess reagent is
where: present. Zinc, cadmium, and nickel form complexes and
consume reagent but do not interfere when sufficient reagent is
C = µg NaCl interpolated from calibration curve, and
present.

12
 E291 − 09
61. Reagents 63.2 To both sample and reference solutions add reagents as
61.1 Ammonium Acetate-Acetic Acid Solution—See Practice in 62.1. Dilute to volume, mix thoroughly, and let stand 15
E200. min.
61.2 Ammonium Hydroxide (1 + 1)—Mix equal volumes of 63.3 Measure absorbance of the sample solution versus the
concentrated ammonium hydroxide (NH4OH, sp gr 0.90) and reference solution as in 62.2.
water.
64. Calculation
61.3 Congo Red Indicator Paper.
64.1 Convert the photometric reading of the test solution to
61.4 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- milligrams of iron by means of the calibration curve. Calculate
chloric acid (HCl). the µg/g of iron as follows:
61.5 Hydroxylamine Hydrochloride Solution (100 g/L)— ~ A 3 1000!
Dissolve 100 g of hydroxylamine hydrochloride (NH2OH·HCl) Iron, µg/g 5 (19)
B
in water and dilute to 1 L.
where:
61.6 Iron, Standard Solution (1 mL = 0.010 mg Fe)—See A = iron found in 100 mL of final solution mg, and,
Practice E200. B = sample represented in the aliquot taken, g.
61.7 1,10-Phenanthroline (o-phenanthroline) Solution (3
g/L)—See Practice E200. 65. Report
65.1 Report the concentration of iron to the nearest 0.1 µg/g.
62. Preparation of Calibration Curve
62.1 To a series of 100-mL volumetric flasks, pipet 0.5, 1.0, 66. Precision and Bias
2.0, 3.0, and 5.0-mL portions of standard iron solution. To each 66.1 The following criteria should be used for judging the
flask add the following reagents in order, mixing after addition acceptability of results (Note 12):
of each 20 mL of water, 5 mL of hydroxylamine hydrochloride 66.1.1 Repeatability (Single Analyst)—The coefficient of
solution, and NH4OH (1 + 1) as required to bring the pH to 3.5 variation for a single determination has been estimated to be
to 4.0 (just alkaline to Congo red paper as an external 5.34 % relative at 98 df. The 95 % limit for the difference
indicator). Add 5 mL of ammonium acetate-acetic acid buffer between two such runs is 15 % relative.
solution, 5 mL of 1,10-phenanthroline solution, dilute to the 66.1.2 Laboratory Precision (Within-Laboratory, Between-
mark with water, mix thoroughly, and allow to stand approxi- Days Variability)—The coefficient of variation of results (each
mately 15 min. Prepare a reference solution in another flask the average of duplicates), obtained by the same analyst on
with water and the same reagents as previously indicated. different days, has been estimated to be 5.6 % relative at 49 df.
62.2 Measure the absorbances of the solutions using an The 95 % limit for the difference between two such averages is
absorption cell with a 5-cm light path (Note 11) and a 16 % relative.
photometer (see 4.1) with a wavelength setting of 510 nm (or 66.1.3 Reproducibility (Multilaboratory)—The coefficient
a filter in the range from 500 to 525 nm). Adjust the photometer of variation of results (each the average of duplicates), ob-
to read zero absorbancy on the reagent blank. tained by analysts in different laboratories, has been estimated
to be 10.4 % relative at 13 df. The 95 % limit for the difference
NOTE 11—This test method has been written for cells having a 5-cm between two such averages is 29 % relative.
light path. Cells of other dimensions may be used, provided suitable
adjustments can be made in the amounts of samples and reagents used. NOTE 12—These precision estimates are based on an interlaboratory
study on four samples covering the range from 4 to 30 µg/g iron in
62.3 Plot on coordinate paper the absorbances of the cali- potassium hydroxide and sodium hydroxide. One analyst in each of fifteen
bration solutions versus milligrams of iron present per 100 mL laboratories performed duplicate determinations and repeated one day
of solution. later.5 Practice E180 was used in developing these precision estimates.
66.2 Bias—The bias of this test method has not been
63. Procedure determined because of the unavailability of suitable reference
63.1 Into a 400-mL beaker, weigh 40 g of sample to the materials.
nearest 0.1 g. Add 100 mL of water and carefully add HCl (sp
gr 1.19) in increments until 50 mL have been added if the SULFATE
sample is 45 % KOH or 50 % NaOH, 75 mL if the sample is
67. Scope
73 % NaOH, or 100 mL if the sample is anhydrous NaOH or
anhydrous KOH. Cover with a watchglass, heat to boiling, and 67.1 This test method covers the gravimetric determination
boil for 1 min. (Any red residue of Fe2O3 should disappear of sulfate present in caustic soda or caustic potash. The lower
during the boiling period.) Cool the solution to room limit of determination is 0.002 g.
temperature, transfer to a 500-mL volumetric flask, dilute to
volume with water, and mix. Pipet an aliquot to contain from 68. Summary of Test Method
0.005 to 0.050 mg of iron into a 100-mL volumetric flask. Into 68.1 Sulfate is determined gravimetrically by precipitation
another 100-mL volumetric flask put 50 mL of water and 1 mL as barium sulfate which is filtered off, washed, ignited, and
of HCl (sp gr 1.19) for a reference solution. weighed.

13
 E291 − 09
69. Reagents where:
69.1 Barium Chloride Solution (120 g BaCl2·2H2O/L)—See A = mass of crucible and precipitate after ignition,
Practice E200. B = mass of empty crucible, and
W = mass of sample used, g.
69.2 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
chloric acid (HCl). 71.2 Calculate the % mass of sodium or potassium sulfate as
follows:
69.3 Methyl Orange Indicator Solution (1 g/L)—See Prac-
tice E200. Sodium sulfate, % mass 5 percent sulfur trioxide 3 1.7741 (21)

69.4 Silver Nitrate Solution (5 g/100 mL)—Dissolve 5 g of Potassium sulfate, % mass 5 percent sulfur trioxide 3 2.1766 (22)
silver nitrate (AgNO3) in water and dilute to 100 mL.
72. Report
70. Procedure
72.1 Report the % mass of the sulfur trioxide to the nearest
70.1 Use Table 7 as a guide to the size of sample to be used. 0.001 %.
70.2 Weigh the sample in a 600-mL beaker to the nearest 0.1
g. Add 300 mL of water and mix. Add 2 to 4 drops of methyl 73. Precision and Bias
orange indicator solution and acidify carefully with HCl adding 73.1 The following criteria should be used for judging the
3 mL in excess of that required to neutralize the sample. acceptability of results (Note 13).
Examine the solution at this point. If it contains any insoluble 73.1.1 Repeatability (Single Analyst)—The standard devia-
matter, filter off on a retentive filter paper. Return the filtrate to tion for a single determination has been estimated to be
the beaker and heat to boiling. Add slowly, with constant 0.00064 % absolute at 88 df. The 95 % limit for the difference
stirring, 25 mL of BaCl2 solution. Digest for 30 min on a steam between two such runs is 0.0018 % absolute.
bath and allow the precipitate to settle overnight at room 73.1.2 Laboratory Precision (Within-Laboratory, Between-
temperature. Days Variability)—The coefficient of variation of results (each
70.3 Filter on ashless, fine quantitative paper and transfer the average of duplicates), obtained by the same analyst on
the precipitate quantitatively to the paper with a fine stream of different days, has been estimated to be the value given in
hot water from a wash bottle. Wash the precipitate with Table 8 at the indicated degrees of freedom. The 95 % limit for
successive small portions of hot water until the washings are the difference between two such averages is also given in Table
free of chloride on testing with 3 to 4 drops of AgNO3 solution. 8.
70.4 Heat a platinum or porcelain crucible to 850 to 900°C 73.1.3 Reproducibility (Multilaboratory)—The coefficient
for 15 min, cool in a desiccator, and weigh to the nearest of variation of results (each the average of duplicates), ob-
0.0001 g. Fold the washed filter paper with precipitate and tained by analysts in different laboratories, has been estimated
place in the tared crucible. Dry and char carefully without to be the value given in Table 8 at the indicated degrees of
flaming. Ignite at 850 to 900°C for a minimum of 30 min. freedom. The 95 % limit for the difference between two such
Remove the crucible from the furnace, allow to cool partially, averages is also given in Table 8.
place in a desiccator, and cool to room temperature. Reweigh NOTE 13—These precision estimates are based on an interlaboratory
to the nearest 0.0001 g. study on three samples containing approximately 0.01, 0.05, and 0.1 %
sulfur trioxide. The number of laboratories analyzing each sample ranged
71. Calculation from twelve to fifteen with one analyst in each performing duplicate
determinations and repeating one day later.5 Practice E180 was used in
71.1 Calculate the percentage of sulfur trioxide as follows: developing these precision estimates.
~ A 2 B ! 3 0.34302 73.2 Bias—The bias of this test method has not been
Sulfur trioxide, % mass 5 3 100 (20)
W
determined because of the unavailability of suitable reference
TABLE 7 Sample Size for Sulfate Analysis materials.
Sample Sample Size, g
45 % KOH 45 to 55
74. Keywords
50 % NaOH 45 to 55 74.1 caustic soda; caustic potash; chloride; iron; potassium
73 % NaOH 30 to 40
Anhydrous KOH and NaOH 20 to 30 carbonate; potassium hydroxide; sodium carbonate; sodium
hydroxide; sulfate; total alkalinity

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 E291 − 09
TABLE 8 Precision for Sulfate Determination
Laboratory Precision Reproducibility
Level, % SO3 Coefficient of Degrees of 95 % Range, Coefficient of Degrees of 95 % Range,
Variation Freedom Percent Relative Variation, % Freedom Percent Relative
0.100 6 14 17 11 13 31
0.050 9 13 25 25 12 70
0.010 12 14 39 30 13 84

SUMMARY OF CHANGES

Subcommittee E15.01 has identified the location of selected changes to this standard since the last issue
(E291-04) that may impact the use of this standard.

(1) Updated units of measure to comply with the International (2) Added Summary of Changes section.
System of Units (SI).

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